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(NoMode1.)' HENRI JOSEPH ERNEST HENNEBUTTEflv CHARLES JUST FELIX RAOULDE JANNEL MENARDJIGOMTB v DE VAUREAL.

PROCESS OF TREATING AMMONIAUAL LIQUORS. No. 259.145. 1 Patented June6,1882% N. PETERS. PhokrLilhngnphar. Wllhin'lon. D, C.

' UNITE STATES I PATENT OFFICE.

HENRI JOSEPH ERNEST HENNEBUTTE, OF ANGLET, AND CHARLES JUST FELIX RAOULDE JANNEL MENARD, VIGOMTE DE VAUREAL, OF BIAR- RITZ, FRANCE,ASSIGNORSKTO THE SOOIETE ANONYME DES PRODUITS GHIMIQUES DU SUD-QUEST, OFPARIS, FRANCE.

PROCESS OF T REATING AMMONIACAL LIQUORS.

SPECIFICATION forming part of Letters Patent No. 259,145, dated June 6,1882,

Application filed November 8, 1881. (No specimens.) Patented in FranceApril 27, 1378, No. 124,137; in England October 29, i878,

' No. 4,353, and July 19, 1880, No. 2,963; and in Germany May, 1879, No.8,171.

. To all whom it may concern:

Be it known that we, HENRI JosEPH ER.- NEST HENNEBUTTE.EI.H(1 CHARLESJUsT FE- LIX BAOUL DE J ANNEL MENARD, Vicomte de Vaural, citizens of theRepublic of France,

residing, the former at Anglet, the, latter at Biarritz, in theDepartment of the Basses Pyr nes and Republic of France, have inventednew and useful Improvements in Process of Treating Ammoniacal Liquors,of which the following is a specification.

This invention relates to a process of treating ammoniacalliquors-suchas the waste waters or'sluice-waters from gas-works and otherfactories-to produce therefrom salts of ammonia; and it consists inexposing said waters to the action of reagents to form a soluble salt orsalts of ammonia, decanting the liquor economic meansfor the productionof sulphate or muriate of ammonia, or concentrated solutions of thesesalts, from their waste waters or sluice-waters.

The treatmentof the ammoniacal waters consists in simply fixing theammonia and evaporating the liquid. The apparatus used is shown in theannexed'drawing. The ammoniacal sluice-waters are led into an openwooden barrel, A, or other suitable receptacle of a capacitycorresponding to the capacity of the works. The barrel is provided witha wooden faucet at about one-third of its height from the bottom of thebarrel. To the ammoniacal liquid in this receptacle is added a reagentin quantities proportioned to the richness of the ammoniacal liquorsoperated on. .If the result desired is to obtain sulphate of ammonia, orconcentrated solutions of sulphate of ammonia,

the reagent employed is sulphate of alumina, either pure or impure.Crude sulphate of alumina-known in England as alum cake. 0 is thoroughlyfit for this purpose. If, on the contrary, it is desired to producechlorhydrate of ammonia or concentrated solutions of chlorhydrate ofammonia, the reagent to be employed will be a mixture of the chlorides0t calcium and iron. This last reagent can be economically obtainedwithout the employment of heat by the following process: In an earthenvessel chlorhydric acid of about 20 or 22 Baum is caused to react oniron ore of a susceptible nature and which has been previously reducedto powder. At the close of twenty four hours the liquid-which is amixture of chloride of iron and, for a large part, of free chlorhydricacid-is decanted into a sec- 0nd receptacle, where the neutralization iseffected by pieces of carbonate of lime. The re sult of the operation isa mixture of the chlorides of calcium and iron of from 40 to 42 Baum.The mixed chlorides of calcium and iron (mixture of chloride of calciumand of chloride of iron) can be obtained by the action upon iron ofchlorhydric acid, which action is made to take place, so that at leasttwo-thirds of the acid employed remains free, 7 5 this excess of acidbeing then saturated by carbonate of lime. lndustrially, two superposedbatteries are formed, consisting of jars of stone or earthenware. Thereceivers of the upper battery contain iron waste; those of the lowerbattery carbonate of lime. The chlorhydric acid is .led into the firstreceivers, where it is allowed tov remain for some hours. Then theliquid resulting from this first operation, and which is a mixture ofchloride of iron and of free acid, is led into the carbonate of lime forcomplete saturation of the excess of acid. The final product of thesetwo successive operationsis a solution of about 40 Baum, the conditionof which is very fao vorable as well for economy of transportation asfor the special use for which it is destined.

In order that the desulphuration of the ammoniacal waters from the gasmay take place under favorable conditions, it sufiices that the reagentin question contains from twenty-five to thirty-three per cent. ofchloride of iron, and in this estimation the proportion of lime of thechlorides may vary without inconvenience-that is to say, that thereagent may show from twenty-five to thirty-three per cent. chloride ofiron and sixty-six to seventy-five per cent. of chloride of calcium. Asshown, the mixture of chloride of calcium and of iron is thus obtainedindustrially by the incomplete attack of the iron, followed by asaturation of the excess of free acid by the carbonate of lime.

The reaction of the sulphate ofalumina upon the ammoniacal sluice-watertakes place as follows: The ammoniacal salts which the water containsreact on the sulphate of alumina to form sulphate of ammoniain solution,while carbonic and sulphhydric acids are set free and a copiousprecipitate of hydrate of alumina is formed, which purifies thesluice-water by carrying with it tarry matter. As to the employment ofthe mixed chlorides of iron and calcium, it gives rise to this otherreaction The chloride of calcium is decomposed by the sesquicarbonate ofammonia of the sluice-water into carbonate of lime, which precipitates,and a chlorhydrate of ammonia, which rests in solution in the liquor.The chloride of iron is attacked at the same time by the sesquicarbonateand sulphhydrate of ammonia to form chlorhydratc of ammonia in solutionand sulphide ofiron, as well as hydrate ofiron, which settle. Afterstanding for twenty-four hours the wooden barrel contains a precipitatecovered by a limpid liquor which contains sulphate or muriate ofammonia, according to the nature of the reagent employed. This liquor,which is decanted in opening the wooden faucet with which the barrel isprovided, is evaporated to the degree desired either in a flatsheet-metal vessel, which is placed upon furnaces, or in a smallsheet-metal vessel, B, placed on the blast-chimney D of the works, or ina sheet-metal vessel heated directly by a fire,if the works have notsufficiently utilizable spent heat.

The concentrated solutions of sulphate or muriate of ammonia aredisposed of in a similar manner as at ammoniacal-salt factories, unlessit should be desired to continue the concentration further andcrystallize the solutions by exposure to cold. From these salts it isalso possible to obtain ammonia by processes well known.

The concentration in sheet-metal vessels of the liquid containingmuriate of ammonia is rendered possible by adding to the solution in thesheet metal vessel a small quantity of double chloride of ammonium andlead. This mixed chloride may be kept ready for use in the vessel 0,provided with afaucet. The object of this double chloride is to preservethe sheet-metal vessel or boiler against the action of the chloride ofammonium (muriate of ammonia) by causing to be deposited on the walls ofthe boiler a galvanic layer or lining of free or metallic lead.

What we claim as new, and desire to secure by Letters Patent, is

1. The herein-described process of treating ammoniacal liquors byexposing said liquors to the action of the mixed chlorides of calciumand iron, decanting or collecting the resulting liquor, and evaporatingor concentrating the samle, substantially as and for the purpose setfort 2. The herein-described process of treating ammoniacal liquors byexposing said liquors to the action of reagents, forming a soluble saltor salts of ammonia, decanting or collecting the liquor holding saidsalt or salts in solution, and evaporating or concentrating the same ina sheet-metal vessel or boiler in the presence of mixed chlorides ofammonium and lead, substantially as and for the purpose described.

In testimony whereof we have hereunto set our hands and seals in thepresence of two subscribing witnesses.

HENRI JOSEPH ERNEST HENNEBUTTE. [L. 8.] CHARLES JUST FELIX RAOUL DEJANNl lL MENARD, VIOOMTE DE VAUREAL. [L. 8.]

WVitnesses:

RENE FRANo, ELYsEE LEON.

